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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 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 Percolation approach to film formation from surfactant-free polystyrene particles(Taylor & Francis, 2005-09) Uğur, Şaziye; Pekcan, Mehmet ÖnderIn this study, a film formation process from surfactant-free polystyrene (PS) latex particles is reported. Steady state fluorescence (SSF) and photon transmission (UVV) techniques were used to study the evolution of film formation. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at time intervals of 2.5 min above the glass transition temperature (T-g) of PS. During the annealing processes, the transparency of the film changed considerably. Fluorescence intensity (I-0P) from P was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored by using photon transmission intensity, I-tr. A drastic increase in I-tr and I-0P above the critical annealing times, t(r) and t(c) were attributed, respectively to percolation behavior of PS material from one side to the other side of the latex film. Critical exponents, beta of percolation clusters were measured and found to be around 0.35 and 0.25 for I-tr and I-0P 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 critical behaviour in N-isopropyl acrylamide gels by using fluorescence technique(Taylor & Francis Group, 2006-11) Kaya Aktaş, Demet; Pekcan, Mehmet ÖnderThe steady state fluorescence (SSF) technique was used to study the sol-gel transition for the solution free radical crosslinking copolymerization of N-isopropyl acrylamide (NIPA), with N,N'-methylenebis (acrylamide) (BIS) as crosslinker in the presence of ammonium persulfate (APS) as an initiator. Pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt, HPTS) was used as a floroprobe for monitoring the polymerization. Pyranine molecules start to bind to NIPA polymer chains upon the initiation of the polymerization, thus the spectra of the bonded pyranines shift to the shorter wavelengths. The get fraction exponent beta and the weight average degree of polymerization exponent gamma' agree best with the mean-field (Flory-Stockmayer) results near the gel point for various crosslinker contents.Yayın Monitoring diffusion of reptating polymer chains by a direct energy transfer method: A Monte Carlo simulation(Wiley-Blackwell, 2002-07-29) Tüzel, Erkan; Kısacıkoğlu, Kemal Batuhan; Pekcan, Mehmet ÖnderA kinetic Monte Carlo method was used to simulate the diffusion of reptating polymer chains across an interface. A time-resolved fluorescence technique in conjunction with a direct energy transfer method was used to measure the extent of diffusion of dye-labeled reptating polymer chains. The diffusion of donor- and acceptor-labeled polymer chains between adjacent compartments was randomly generated. The fluorescence decay profiles of donor molecules were simulated at several diffusion steps to produce mixing of the polymer chains. Mixing ratios of donor- and acceptor-labeled polymer chains in compartments were measured at various stages (snap-shots) of diffusion. It was observed that for a given molecular weight, the average interpenetration contour length was found to be proportional to the mixing ratio. Monte Carlo analysis showed that the curvilinear diffusion coefficient is inversely proportional to the weight of polymer chains during diffusion.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 Sorption and slow release kinetics of PAAM gels at various temperatures(Freund Publishing House Ltd, 2007-11) Akın Evingür, Gülşen; Pekcan, Mehmet ÖnderSmall molecule sorption and slow release in and out of polyacrylamide (PAAm) gels were studied by using steady state fluorescence (SSF) technique. Pyranine (P-y) dissolved in water used as a probe. Fluorescence emission intensity, I-p from P-y was used to monitor for studying sorption and slow release processes at various temperatures. Sorption and slow release processes were analyzed by using Fickian diffusion model and coefficients were obtained. Related activation energies were also calculated for the corresponding physical processes.
