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Yayın Photon transmission study on conformational ordering of iota-carrageenan in CaCl2 solution(Taylor & Francis Inc, 2005-06) Kara, Selim; Pekcan, Mehmet ÖnderCoil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of iota-carrageenan in CaCl2 solution upon cooling were studied using photon transmission technique. Photon transmission intensity, I-iota r was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (T-ch and T-hd) and activation energies (Delta E-ch and Delta E-hd). An extra dimer-to-dimer (d-d) transition was also observed during cooling at low temperature region. However, upon heating dimers disappear to double helices by making dimer-to-double helix (d-h) transition. Further heating resulted double helix-to-coil (h-c) transition at high temperature region. T-dh and T-ch temperatures and Delta E-dh and Delta E-hc activation energies were also determined. It was observed that T-hc and T-ch temperatures and Delta E-dh and Delta E-hd activation energies do not effected by carrageenan content. However, T-hd, T-dh and T-dd temperatures and Delta E-ch and Delta E-hc activation energies were found to be strongly correlated to the carrageenan content in the system.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 Cation effect on gel-sol transition of kappa carrageenan(Springer, 2008-04) Pekcan, Mehmet Önder; Tarı İlgin, ÖzlemThe steady state fluorescence (SSF) technique was employed to study gel - sol transitions of kappa carrageenan in NaCl, KCl and CaCl2 solutions. Pyranine was used as a fluorescence probe for monitoring these transitions. Scattered light, I-sc and fluorescence intensity, I was monitored against temperature to determine the gel - sol (T-gs) transition temperatures and exponents. It was observed that T-gs values are strongly correlated to the NaCl, KCl and CaCl2 contents. The weight average degree of polymerization, DPw and gel fraction G, exponents (gamma and beta) were measured and found to be in accord with the classical Flory-Stockmayer Model.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 Synergistic effect of the locust bean gum on the thermal phase transitions of kappa-carrageenan gels(Elsevier Sci Ltd, 2009-03) Arda, Ertan; Kara, Selim; Pekcan, Mehmet ÖnderSynergism between K-carrageenan and locust bean gum (LBG) was studied using the photon transmission technique. Synergistic effects in these polymeric mixtures strongly affected the physical properties of the gel structure. The transmitted light intensities, I-tr, versus temperature variations were investigated during the gelation and liquefaction processes. Slight synergistic peaks were detected in gel-sol and sol-gel transition temperatures for high kappa-carrageenan/LBG ratios (approx. 80/2). Moreover, apparent synergistic peaks were observed in gel-sol and sol-gel transition activation energies for the mixtures approximately with the ratios of 80/10.Yayın Critical behavior of thermal phase transitions of iota-carrageenan in CaCl2 solution(Elsevier B.V., 2006-07-15) Özbek, Haluk; Pekcan, Mehmet ÖnderIn situ photon transmission method was applied to study thermal phase transitions of ?-carrageenan in CaCl2 solution. Coil-to-helix (c-h) and helix-to-dimer (h-d) transitions were detected upon cooling. An extra dimer-to-dimer (d-d) transition was observed as well during cooling at low-temperature region. Upon heating only dimer-to-helix (d-h) and helix-to-coil (h-c) transitions were detected. Photon transmission intensity, Itr was monitored against temperature to determine several phase transitions and transition temperatures. It was observed that the c-h transition in ?-carrageenan-CaCl2 system performs a crossover between 3D percolation to classical theory. Upon heating, the specific heat exponent over the d-h transition was extracted from the transmitted intensity data and was found to be 0.045.Yayın Universal behaviour of glass transition exponents in various polymeric systems(VSP BV, Brill Academic Publishers, 2005) Pekcan, Mehmet Önder; Kaya Aktaş, DemetThe fast transient fluorescence (FTRF) technique was used to study the critical exponents during glass transition in free-radical cross-linking copolymerization (FCC). Methyl methacrylate (MMA), ethyl methacrylate (EMA) and various combinations of MMA with EMA were used during FCC experiments. Pyrene (Py) was used as a fluorescence probe and its fluorescence lifetimes from its decay traces were measured during glass transition. Changes in the viscosity of the pre-gel solutions due to glass formation dramatically increased the Py fluorescent lifetimes, which were used to study the glass transition of MMA, EMA and their mixtures as a function of time, at various temperatures and monomer concentrations. The results were interpreted in the view of percolation theory. The critical exponents, beta and gamma, were measured near the glass transition point and found to be around 0.37 +/- 0.015 and 1.69 +/- 0.05, respectively, in all systems studied, which are in good agreement with the static percolation results.Yayın Phase transitions of kappa-carrageenan gels in various types of salts(John Wiley & Sons Inc, 2006-11-05) Kara, Selim; Arda, Ertan; Kavzak, Burhan; Pekcan, Mehmet ÖnderSol-gel and gel-sol phase transitions of K-carrageenan in various types of salts were studied using photon transmission technique. Here, LiCl, NaCl, KCl, MgCl2, CaCl2, and SrCl2 were chosen as the proper salts for the K-carrageenan-water system. Photon transmission intensity, I-tr was monitored against temperature to determine the sol-gel and gel-sol temperatures (T-sg and T-gs) and activation energies (Delta E-sg and Delta E-gs). It was observed that T-gs temperatures were notably higher than T-sg due to the hysteresis on the phase transition loops. It was observed that stronger carrageenan gels are formed in the presence of KCl compared to the others.Yayın Molecular recognition during sol-gel and gel-sol transition of kappa-iota carrageenan mixtures(Taylor & Francis ltd, 2005-12) Kara, Selim; Arda, Ertan; Pekcan, Mehmet ÖnderSol-gel and gel-sol phase transitions of kappa-iota (kappa-iota) carrageenan mixtures in two types of salts were studied using photon transmission technique. Here, KCl and CaCl2 were chosen as the proper salts for the carrageenan mixtures. Coil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of carrageenan mixtures in monovalent and bivalent cation solutions were studied upon heating and cooling by using photon transmission technique. Photon transmission intensity, It, was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (T-ch and T-nd). Two distinct transition regions were observed in both heating and cooling of the carrageenan-bivatent CaCl2 salt system. At the first step of heating process dimers decompose into double helices by making (d-h) transition. At the high temperature region (h-c) transition takes place. Carrageenan-monovalent KCl salt system presented only (c-h) and (h-c) transitions upon cooling and heating processes. Transition temperatures at the heating and cooling processes were obtained. A hysteresis was observed between (h-c)-(c-h) and (d-h)-(h-d) transitions for the monovalent and bivalent cations respectively.
