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Yayın Small molecule sorption and desorption in and out of iota-carrageenan gels(Taylor & Francis Group, 2007-08) Ataman, Evren; Pekcan, Mehmet ÖnderSmall molecule sorption and desorption in and out of Iota-Carrageenan was studied by using steady-state fluorescence (SSF) technique. Pyranine dissolved in water used as fluorescence probe. Fluorescence emission intensity, I-p from pyranine was monitored for studying sorption and desorption processes at various temperatures. The Fickian model was applied to produce sorption, D-s, early desorption, D-ed, and desorption, D-d, coefficients. Corresponding activation energies were obtained and found to be 20.5 kJ mol(-1), 7.0 kJ mol(-1) and 34.9 kJ mol(-1), respectively. The observed D-ed value is an order of magnitude smaller than the D-s and D-d coefficients. On the other hand, sorption processes were shown to be twice as fast as desorption processes.Yayın Temperature effect on drying and swelling of kappa carrageenan gels: A steady state fluorescence study(Wiley-V C H Verlag GMBH, 2008) Tarı İlgin, Özlem; Pekcan, Mehmet ÖnderA novel technique based on in situ steady state fluorescence (SSF) measurements is introduced for studying drying and swelling Of kappa(-) carrageenan (kappa carrageenan) gels at various temperatures. kappa(-) carrageenan gels were completely dried and then swelled in water vapor. Pyranine was embedded in kappa(-) carrageenan and used as a fluorescence probe. Scattered light intensities, I-SC and fluorescence intensities, I were monitored during the drying and swelling Of kappa(-) carrageenan gels. it was observed that the fluorescence intensity decreased linearly as drying time was increased. A simple model consisting of Case II diffusion was used to quantify the drying processes of the kappa(-) carrageenan gels. This moving boundary model provided packing constant, kappa(o). During swelling, fluorescence intensity increased exponentially as time is increased. The increase in I, was modeled using Li-Tanaka equation from which swelling time constants, tau(c) and cooperative diffusion coefficients, D-c were determined. It was observed that swelling time constants, tau(c) decreased and diffusion coefficients, D-c increased as the swelling temperature was increased. Activation energies for drying and swelling were also obtained and found to be 53.9 and 47.2 kJ mol(-1), respectively.Yayın Monovalent and divalent cation effects on phase transitions of iota-carrageenan(Sage Publications Ltd, 2007-01) Kara, Selim; Arda, Ertan; Pekcan, Mehmet ÖnderPhase transitions Of L-carrageenan in a variety of monovalent (Li, Na, K) and divalent (Mg, Ca, Sr) cation solutions were studied during heating and cooling by using photon transmission technique. Photon transmission intensity (I-tr) was monitored against temperature to determine the transition temperatures and activation energies during the heating and cooling processes in the monovalent and divalent systems. Three distinct transition regions were observed during the heating and cooling cycles for the carrageenan-divalent salt system. At the first step of the heating process, dimer groups were transformed into dimers that presented (g-d) transitions, then these dimers were directly converted into a double helix by undergoing a (d-h) transition. In the higher temperature region, a double helix-to-coil (h-c) transition took place. During the cooling process, these transitions are arranged in the order of (c-h), (h-d), and (d-g). The carrageenan-monovalent salt system presented only coil-to-rod-like helix (c-r) and rod-like helix-to-coil (r-c) transitions during the cooling and heating processes, respectively. A hysteresis was observed between (r-c)-(c-r) and (g-d)-(d-g) transitions for the monovalent and divalent cations, respectively.Yayın Molecular alignment during gel formation from methyl methacrylate: An excimer fluorescence study(Taylor & Francis Ltd, 2005-05) Kaya Aktaş, Demet; Erdoğan, Matem; Pekcan, Mehmet ÖnderGlass transition during bulk polymerization was studied in free-radical cross-linking copolymerization (FCC) of methyl methacrylate (MMA) using the steady-state fluorescence (SSF) technique. Naphthalene (N) was used as a monomer and excimer forming probe. Changes in the viscosity of the pregel solutions due to gel formation dramatically enhance both monomer and excimer fluorescent yield of N molecules. The reaction time at which the monomer and excimer intensities exhibit a sudden increase corresponds to the reaction time at which the rate of polymerization becomes maximum resulting from the gel effect. This effect was used to study the gelation of MMA, as a function of time, in various N concentrations. The results were interpreted in the view of percolation theory. The gel fraction, beta, and weight average degree of polymerization, gamma, exponents beta=0.40 +/- 0.02 and gamma=1.70 +/- 0.07 were found in agreement with percolation results for both monomer and excimer measurements, respectively.Yayın In situ fluorescence study of swelling, sorption and desorption processes in and out of PAAm gels(Wiley-V C H Verlag GMBH, 2008-05) Evingür, Gülşen Akın; Karslı, Kadir; Pekcan, Mehmet ÖnderSmall molecule sorption and desorption in and out of polyacrylamide (PAAm) gels were studied at various temperatures. Pyranine (P(y)) dissolved in water used as a probe. Fluorescence emission intensity, I(p) from P(y) was monitored for studying sorption and desorption processes. Scattered light intensities, I(SC) from PAAm gel was also monitored to observed structural variations during sorption and desorption process. Li-Tanaka model was applied to produce the swelling time constants, tau(C) and sorption coefficients, D(C) for the swelling processes. on the other hand, sorption and desorption processes were studied and coefficients were produced by using Fickian model. Related activation energies were also calculated from the corresponding physical processes.Yayın Study on swelling of hydrogels (PAAm) at various temperatures by using fluorescence technique(Springer US, 2007-10) Kaya Aktaş, Demet; Akın Evingür, Gülşen; Pekcan, Mehmet ÖnderSteady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) hydrogels. Disc-shaped gels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with N, N'- methylenebis (acrylamide) (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was measured during in situ swelling process at various temperatures and it was observed that fluorescence intensity values decreased as swelling is proceeded. Li-Tanaka equation was used to determine the swelling time constants, tau(c) and cooperative diffusion coefficients, D-c from intensity, weight and volume variations during the swelling processes. It is observed that swelling time constants, tau(c) decreased and diffusion coefficients, D-c increased as the swelling temperature is increased. The swelling activation energies, Delta E were measured from the intensity, weight and volume variations and found to be 10.7, 32.2 and 64.1 kJ mol(-1), respectively.Yayın Drying of PAAm hydrogels at various temperatures: A fluorescence study(Taylor & Francis Group, 2007-05) Aktaş, Demet Kaya; Evingür, Gülşen Akın; Pekcan, Mehmet ÖnderThe 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, triangle E-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.Yayın Monitoring small molecule diffusion into hydrogels at various temperatures by fluorescence technique(Elsevier B.V., 2006-12-01) Evingür, Gülşen Akın; Karslı, Kadir; Pekcan, Mehmet Öndersteady state fluorescence technique was used to study small molecule diffusion into polyacrylamide (PAAm) gels at various temperatures. Pyranine (P-y), dissolved in water was introduced as a probe and fluorescence emission (I-p) from Py was monitored during diffusion. Scattered light intensities, I-sc from PAAm gel was also monitored to observe structural variations during diffusion process. Increase in I-P intensity was attributed to P-Y diffusion into PAAm get. On the other hand decrease in I-sc intensity was interpreted as the variation of the spatial heterogeneities in the system. Li-Tanaka and Fickian models were used to quantify the swelling and diffusion experiments and diffusion coefficients were produced in both cases. Related activation energies were also calculated from the corresponding physical processes.Yayın Study of drying of kappa-carrageenan gel at various temperatures using a fluorescence technique(Taylor & Francis Inc, 2008-01) Tarı İlgin, Özlem; Pekcan, Mehmet ÖnderThe steady-state fluorescence technique was used to study drying of kappa-carrageenan gel at various temperatures. Pyranine was doped as a fluorescence probe, and scattered light, I-sc, and fluorescence intensities, I, were monitored during drying of these gels. It was observed that I decreased linearly as drying time is increased. The moving boundary model based on Case II diffusion was applied to produce the packing constants, k(0), at higher temperatures. Activation energy for drying was found to be 53.9 kJ mol(-1). Supporting gravimetric and volumetric measurements were also carried out during drying of gels and the corresponding activation energies were determined to be 46.4 and 58.9 kJ mol(-1), respectively.Yayın Reversible film formation from nano-sized PNIPAM particles below glass transition(Springer-Verlag, 2007-01) Uğur, Şaziye; Elaissari, Abdelhamid; Yargı, Önder; Pekcan, Mehmet ÖnderReversible film formation process from nano-sized Poly(N-isopropylacrylamide) (PNIPAM) microgel particles were studied during heating-cooling cycles at various rates. Photon transmission technique was used and transmitted photon intensity I (tr) was monitored during heating-cooling cycles. The increase and decrease in I (tr) during heating and cooling was explained with the void closure and void reconstruction processes, and the corresponding activation energies were measured. It was observed that PNIPAM microgels required less energy during reconstruction of voids than their closure.
