Demet Kaya Aktaş

Elucidation of multiple-point interactions of pyranine fluoroprobe during the gelation

We have studied the multiple-point interactions of the pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt; 3sPyOH) fluoroprobe with polymer chains during the free-radical polymerization of acrylamide (AAm) by using the steady state fluorescence measurements. We observed a considerable blue shift from 515nm to 406nm in the emission spectra due to a C-O ether bond formation between the hydroxylic oxygen of 3sPyOH and a terminal C-atom of the growing AAm chain. Furthermore ionic (electrostatic) interactions occur between the three ionized sulfonic acid groups (SO(3)(-)) of 3sPyOH and protonated amide groups on the AAm chains. These electrostatic interactions also cause a gradual red shift in the maximum of the short-wavelength-peak, from 406nm to 430nm. The results showed that the pyranine can be used as a probe for real time monitoring of the polymerization process of AAm system since it monitors both the progression of the polymerization via chemical binding over OH group and the change in the local density of the polymerizing sample by means of the gradual red shift in the short-wavelength-peak via ionic interactions over SO(3)(-) groups.

Universal behaviour of gel formation from acrylamide-carrageenan mixture around the gel point: a fluorescence study.

Abstract The steady state fluorescence (SSF) technique was used to study the sol-gel transition, for the solution free radical crosslinking copolymerization of acrylamide (AAm) with various carrageenan content. N, N′- methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) are used as crosslinker and an initiator, respectively. Pyranine (8-hydroxypyrene-1, 3,6-trisulfonic acid, trisodium salt, HPTS) was added as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to acrylamide polymer chains upon the initiation of the polymerization; thus, the spectra of the bonded pyranines shift to the shorter wavelengths. Fluorescence spectra from the bonded pyranines allows one to monitor the sol-gel transition, without disturbing the system mechanically, and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the critical point show that the gel fraction exponent β obeyed the percolation result for low carrageenan concentrations (<2.0%) however classical results were produced at higher carrageenan concentration (>2.0%).

Critical Exponents of Gelation and Conductivity in Polyacrylamide Gels Doped by Multiwalled Carbon Nanotubes

Polyacrylamide (PAM) doped by multiwalled carbon nanotube (MWNT) gels were prepared with different amounts of MWNTs varying in the range between 0.1 and 15 wt%. The PAM–MWNT composite gels were characterized by the steady state fluorescence technique (SSF). The alternative electrical conductivity (AC) of PAM–MWNT composite gels was measured by the dielectric spectroscopy technique. Observations around the gel point, t gel for PAM–MWNTs composite gels showed that the gel fraction exponent β obeyed the percolation result. The critical exponent r of AC electrical conductivity for the composite PAM–MWNT gel was also measured and found to be about 2.0, which agrees with a random resistor network.

Steady state fluorescence technique for studying phase transitions in PAAm–PNIPA mixture

The steady state fluorescence (SSF) technique was used to study the sol-gel phase transition during free radical crosslinking copolymerisation of various amounts of acrylamide (AAm) and N-isopropylacrylamide (NIPA) mixtures. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as crosslinker and an initiator, respectively. Pyranine (8-hydroxypyrene-1, 3, 6-trisulfonic acid, trisodium salt, HPTS) was added as a fluoroprobe for monitoring the polymerisation. It was observed that pyranine molecules bind to AAm and NIPA chains upon the initiation of the polymerisation, thus the fluorescence spectra of the bonded pyranines shift to the shorter wavelengths. Fluorescence spectra from the bonded pyranines allowed us to monitor the sol-gel phase transition, without disturbing the system mechanically, and to test the universality of the sol-gel transition as a function of polymer concentration ratios. Observations around the gel point of PAAm–PNIPA mixtures show that the gel fraction exponent β obeyed the percolation result.

Drying of PAAm Hydrogels at Various Temperatures: A Fluorescence Study

The steady‐state fluorescence (SSF) technique was employed for studying the drying of polyacrylamide (PAAm) hydrogels. Disc‐shaped hydrogels were prepared by free‐radical crosslinking copolymerization of acrylamide (AAm) with N,N′‐methylene bisacrylamide (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine (P) was introduced as a fluorescence probe and the intensity of pyranine was monitored during in situ drying at various temperatures. It was observed that the fluorescence intensity of pyranine increased during the drying process. A supporting, gravimetrical experiment was also performed. A phenomenological equation was introduced to determine the desorption coefficient, D, of water molecules from the drying hydrogels at various temperatures. The desorption activation energy, ΔE d, values were measured for the drying processes and found to be 91.08 and 36.82 kJ mol–1 by fluorescence and gravimetrical methods, respectively. This difference most probably originates from the origin of the techniques; the fluorescence technique measures the parameters at a molecular level, whereas the gravimetrical technique measures a parameter in the bulk.