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It is well known that ions affect polymers in specific ways not solely based on electric charge, usually referred to as the Hoffmeister effect or ion specific effects. Poly(N-isopropylacrylamid) (PNIPAM) is a thermosensitive polymer with a LCST at 32℃. PNIPAM is a well studied polymer due to its similarities with denaturation of proteins in aqueous solutions. Utilizing diffusion NMR this report studied the effect different Hoffmeister anion concentrations have on the configuration of pre-transitional PNIPAM. A fractionation process was developed for PNIPAM, yielding a product of about 87 000 g/mol, used for diffusion measurements. Diffusion coefficients for PNIPAM in saline solutions ranging from 0 to 800 mM were measured for NaCl, NaClO4, NaSCN and NaI. Diffusion coefficients for PNIPAM were also measured at some concentrations of NaF, Na2SO4 and Na2CO3. Hydrodynamic radius was calculated from the diffusion coefficients. The report found a pre-transitional chain collapse of PNIPAM which increased with ionic concentrations of NaCl, NaClO4, NaSCN, NaF and Na2CO3, but not for NaI and Na2SO4. At 800 mM the hydrodynamic radius decreased with 9% for NaCl, 13% for NaClO4 and 5% for NaSCN. The hydrodynamic radius decreased with 19% at 300 mM Na2CO3 and with 10% at 400 mM NaF. There was a significant decrease in hydrodynamic radius for high concentrations of NaCl and NaClO4 but exact decrease needs to be replicated to validate the findings due to an unexpected large decrease in hydrodynamic radius already at 50 mM. Values for NaF and Na2CO3 should be replicated with internal standard to accomodate for possible precipitation of the longer polymer chains within the fraction.

Here, we report on a new temperature responsive polymer brush system with a terminal “click” functionality. Bifunctionalized poly(N-isopropylacrylamide) (PNiPAAm) with distinct functional end groups was synthesized by atom transfer radical polymerization (ATRP) and grafted to a modified silicon substrate. The presence of the active terminal alkyne functionality is validated using an azide-modified rhodamine B (N3-RhB) via copper(I) catalyzed alkyne–azide cycloaddition (CuAAC). The optical properties and swelling dynamics of an N3-RhB modified PNiPAAm brush are analyzed in dry state and in situ by VIS-spectroscopic ellipsometry (SE). The best-fit results are obtained using a Gaussian oscillator model and are confirmed by UV/VIS-spectroscopy. We observed evidence of interactions between the aromatic residues of the dye and the PNiPAAm amide groups, which significantly affect the swelling behavior of the modified polymer brush. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Here, we report on a new temperature responsive polymer brush system with a terminal “click” functionality. Bifunctionalized poly(N-isopropylacrylamide) (PNiPAAm) with distinct functional end groups was synthesized by atom transfer radical polymerization (ATRP) and grafted to a modified silicon substrate. The presence of the active terminal alkyne functionality is validated using an azide-modified rhodamine B (N3-RhB) via copper(I) catalyzed alkyne–azide cycloaddition (CuAAC). The optical properties and swelling dynamics of an N3-RhB modified PNiPAAm brush are analyzed in dry state and in situ by VIS-spectroscopic ellipsometry (SE). The best-fit results are obtained using a Gaussian oscillator model and are confirmed by UV/VIS-spectroscopy. We observed evidence of interactions between the aromatic residues of the dye and the PNiPAAm amide groups, which significantly affect the swelling behavior of the modified polymer brush. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.