Biomedical subjects

Onder Pekcan

Publications and source records attributed to Onder Pekcan.

16 recordsLinked to original sources

PubMed2006

Monitoring small molecule diffusion into hydrogels at various temperatures by fluorescence technique.

Steady 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 P(y) 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 gel. 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.

Biophysics↗

PubMed2006

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

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 beta obeyed the percolation result for low carrageenan concentrations (< 2.0%) however classical results were produced at higher carrageenan concentration (> 2.0%).

Acrylamide↗

PubMed2005

Vapor-induced film formation from low-Tg particles for different solvent compositions.

The photon transmission method was used to study latex film formation from poly(vinyl acetate) (PVAc) particles induced by two different solvents. Films with the same latex content were prepared from PVAc particles and exposed to vapor of ethanol-water and acetone-water mixtures in various compositions. Transmitted photon intensities, Itr, from these films increased with increasing vapor exposure time. The increase in Itr is attributed to the increase in crossing density at the polymer-polymer junction. The Prager-Tirrell model was employed to obtain the back-and-forth frequency, nu, of the reptating polymer chain during film formation induced by solvent vapor. It was observed that the produced nu values increase as the solvent content is increased for both solvents. Abilities of both solvents to form films were interpreted with the solubility parameters of the solvents and the PVAc.

Journal Article↗

PubMed2005

Film formation from pure and mixed latices; transient fluorescence study.

A fast transient fluorescence technique was used to study latex film formation induced by organic solvent vapor. Mixtures of pyrene (P)- and naphthalene (N)-labeled and/or pure naphthalene-labeled latex films were prepared separately from poly(methyl methacrylate) (PMMA) particles. Then these pure and mixed latex films were exposed to vapor of various chloroform-heptane mixtures in seven different experiments. In both films, fluorescence lifetimes from N were monitored during vapor-induced film formation. It was observed that N lifetimes decreased as the vapor exposure time is increased. A Stern-Volmer kinetic analysis was used for low quenching efficiencies to interpret the decrease in N lifetimes. A Prager-Tirrell model was employed to obtain back-and-forth frequencies, nu, of reptating PMMA chains during latex film formation induced by solvent vapor. In both pure and mixed latex films, nu values were found to be correlated with the chloroform content in the vapor mixture. It was observed that polymer interdiffusion obeyed a t1/2 law during film formation.

Journal Article↗

PubMed2005

Photon transmission study on conformational ordering of iota-carrageenan in CaCl2 solution.

Coil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of iota-carrageenan in CaCl(2) solution upon cooling were studied using photon transmission technique. Photon transmission intensity, I(tr) was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (T(ch) and T(hd)) and activation energies (DeltaE(ch) and DeltaE(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 DeltaE(dh) and DeltaE(hc) activation energies were also determined. It was observed that T(hc) and T(ch) temperatures and DeltaE(dh) and DeltaE(hd) activation energies do not effected by carrageenan content. However, T(hd), T(dh) and T(dd) temperatures and DeltaE(ch) and DeltaE(hc) activation energies were found to be strongly correlated to the carrageenan content in the system.

Calcium Chloride↗

PubMed2005

Cation effect on thermal transition of iota-carrageenan: a photon transmission study.

Coil-to-double helix (c-h) and double helix-to-dimer (h-d) phase transitions of iota-carrageenan in various cation (CaCl2) solutions upon heating and cooling were studied using the photon transmission technique. Photon transmission intensity, Itr, was monitored against temperature to determine the (c-h) and (h-d) transition temperatures (Tch and Thd) and activation energies (DeltaEch and DeltaEhd). An extra dimer-to-dimer (d-d) transition was observed during cooling at low temperature region. However, upon heating dimers directly decompose into double helices by making dimer-to-double helix (d-h) transition. Further heating results in double helix-to-coil (h-c) transition at high temperature region. Tdh and Thc temperatures and Delta Edh and DeltaEhc activation energies were determined. It was observed that Thc and Tch temperatures and DeltaEch and DeltaEhc activation energies were found to be strongly correlated to the CaCl2 content in the system.

Biocompatible Materials↗

PubMed2004

The effect of annealing temperature on latex film dissolution.

The steady-state fluorescence technique (SSF) was used to study the dissolution of polystyrene (PS) latex films in toluene. The main objective of this study was to explore the effects of annealing temperature on the dissolution behavior of the PS films. It has been shown that dissolution coefficients of PS films are highly affected by the annealing temperatures. It was found that, while PS films dissolved as entangled clusters when annealed at low temperatures, they dissolved as individual chains at high annealing temperatures. The results showed that when the annealing temperature increases, the dissolution takes place in the disentanglement regime. The decrease in dissolution coefficients, Dd, can be explained as a shift of dissolution from the entangled clusters regime to the disentanglement regime. The measured Dd values were found to be in between 4.2 and 1.0 x 10(-10) cm2 s(-1) for an annealing temperature range of 110-220 degrees C.

Fluorescence↗

PubMed2004

Scaling of thermal hysteresis at nematic-smectic-A phase transition in a binary mixture.

The photon transmission method was applied to study the scaling of thermal hysteresis at the nematic-smectic-A transition in a binary mixture of 4-ethoxy-4(')-(6-vinyloxyhexyloxyl) azobenzene monomer, smectogen, and 4-hexoxy-3(')-methly-4(')-(6-acryloyloxyhexyloxy) azobenzene. The thermal hysteresis loops were obtained under linearly varying temperature. It has been found that the area A of the hysteresis loops scales with the temperature scanning rate R as A=A(0)+bR(n) with the exponent n equal to 0.692, which is consistent with the (Phi(2))(3) field theoretical model value within the experimental resolution.

Journal Article↗

PubMed2004

Direct test of the critical exponents at the sol-gel transition.

The steady state fluorescence technique was used to study the sol-gel transition for the solution-free radical cross-linking polymerization of acrylamide (AAm), with N,N'-methylenebis (acrylamide) as cross linker in the presence of ammonium persulfate as an initiator. Pyranine (8-hydroxypyrene-1, 3,6-trisulfonic acid, trisodium salt) is used as a fluoroprobe 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 such as polymer concentration, cross-linker concentration, and temperature. Observations around the critical point show that there are three regimes for AAm concentration in which the exponents differ drastically. The gel fraction exponent beta and the weight average degree of polymerization exponent gamma agree best with the static percolation results for higher acrylamide concentrations above 1M, but they cross over from percolation to mean-field (Flory-Stockmayer) values when the AAm concentration is lower than 2M. For very low polymer concentrations, below which the system can not form the gel, the exponents differ considerably from both the percolation and the mean-field values.

Journal Article↗

PubMed2004

Can the glass transition in bulk polymers be modeled by percolation picture?

Recent observations (Eur. Phys. J. E 9, 135 (2002)) showed that the vitrification process, which sets in during the linear bulk methyl methacrylate (MMA) polymerization carried out below glass transition temperatures, can be modelled by static percolation picture. To generalize this observation for different kind of bulk linear or crosslinked polymers not enough data are present in the literature. To cover partly this deficit we studied the glass transition of MMA and styrene (Sty) crosslinking copolymerization in varying ratios of MMA and Sty. Both the fluorescence intensity I and the lifetime tau of pyrene (Py) used as a nanosecond in situ fluoroprobe were monitored during the gelation time. Both I and tau increase dramatically as a result of the reduced mobility of the probes trapped in the "glassy" regions, appearing near the glass transition point. The average size of the glassy regions just below, and the strength of the infinite network formed upon the connection of the glassy regions above the glass transition point tg obey power law relations. The data around tg were interpreted on the basis of the percolation theory and we observed that the corresponding exponents gamma and beta give static percolation values independent of the polymer composition.

Biophysics↗

PubMed2003

Void closure and interdiffusion processes during latex film formation from surfactant-free polystyrene particles: a fluorescence study.

This study reports a steady state fluorescence (SSF) technique for studying film formation from surfactant-free polystyrene (PS) latex particles. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at elevated temperatures for 5-, 10-, 20-, and 30-min time intervals above the glass transition (T(g)) temperature of polystyrene. During the annealing processes, the transparency of the film changed considerably. Scattered light (I(sc)) and fluorescence intensity (I(0P)) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored using photon transmission intensity, I(tr). Scanning electron microscopy (SEM) was used to detect variation in the physical structure of annealed films. Onset temperature for film formation, T(0), void closure, T(v), and healing temperatures, T(h), were determined and corresponding activation energies were measured. Void closure and interdiffusion stages were modeled and related activation energies were determined.

Journal Article↗

PubMed2003

Cation effects on sol-gel and gel-sol phase transitions of kappa-carrageenan-water system.

Sol-gel and gel-sol phase transitions of kappa-carrageenan in pure water and in KCl solution were studied using photon transmission technique. 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 (deltaH(sg) and deltaH(gs)). It was observed that T(gs) was notably higher than T(sg) due to the hysteresis on the phase transition loops. T(gs) and deltaH(gs) values were also higher for gels containing KCl than for those without KCl. The increase in carrageenan content caused an increase in both critical temperatures and activation energies for the gels prepared in pure water and in KCl solution. Increases in the KCl/carrageenan ratio, raised both T(gs) and T(sg). Similarly deltaH(sg) was elevated by the increase in cation content of the gel. These results were interpreted as the formation of stronger gels in the presence of KCl in water.

Carrageenan↗

PubMed2003

Cation effects on swelling of kappa-carrageenan: a photon transmission study.

Swelling behavior of kappa-carrageenan gels in water and KCl solutions was investigated by photon transmission experiments following the preparation of gels in the presence and absence of externally added K+ ion as a gel promoting agent. Transmitted photon intensity, Itr, increased continuously during swelling depending on the carrageenan and ion content in the gel. This increase in Itr was modeled using the Li-Tanaka equation. Both the experimental work and the model showed that the swelling of low carrageenan and ion content gels took less time than that of high ion content gels. It is confirmed that double helices in a swollen gel move much faster in pure water than in KCl solution during swelling processes. Swelling time constants, tau1, and collective diffusion coefficients, Do, were measured for the gels swollen in water and KCl solutions.

Carrageenan↗

PubMed2003

Photon transmission study on swelling of kappa-carrageenan gels prepared in various concentrations.

kappa-Carrageenan gels prepared with various carrageenan concentrations in pure water were completely dried and then swelled in pure water. Photon transmission measurements were performed using a UV-Vis (UVV) spectrometer during the swelling of kappa-carrageenan gels. Transmitted photon intensity, I(tr), increased exponentially as swelling time is increased for all gel samples. The behaviour of I(tr) was interpreted by Monte-Carlo Simulation. The increase in I(tr) was quantified by employing Li-Tanaka equation, from which time constants tau(1) and collective diffusion coefficients, D(o) were determined for the gels in various carrageenan concentrations. Gravimetric and volumetric measurements were also carried out during swelling of gels. It is observed that gel with high carrageenan content possess more double helices and more lattice dislocations and swell slower than gels with low carrageenan content which may contain less double helices and less lattice imperfections. Increase in I(tr) was interpreted by the homogeneous distribution of double helices in the carrageenan gel system.

Carrageenan↗

PubMed2002

Swelling of interpenetrating networklike particles in a soft polymer matrix.

Fast transient fluorescence technique was used to monitor swelling of hard latex particles in a soft polymer matrix. Various film samples were prepared from pyrene (P) and/or naphthalene (N)-labeled poly(methyl methacrylate) (PMMA) particles in a low-molecular-weight poly(isobutylene) (PIB) matrix. These PMMA particles contain interpenetrating PIB channels. Film samples were annealed at elevated temperatures to promote particle swelling. Fluorescence lifetimes, tau, were measured for each film sample. It was observed that tau values decrease as the PIB content in the matrix is increased. The decrease in tau was explained by the increase in quenching of excited P and N molecules by low-molecular-weight PIB penetrating into the PIB channels in the PMMA particles. A drastic decrease in tau above a certain temperature was attributed to the effect of particle size on the swelling of the latex particles in the PIB matrix. It was observed that small particles (P-labeled) swell at much lower annealing temperatures than large (N-labeled) particles.

Journal Article↗

PubMed2002

Site percolation model for latex film formation in soft polymer matrix.

The UV-visible (UVV) technique was used to monitor latex film formation in a soft polymer matrix. Various film samples were prepared by increasing the amount of poly(methyl methacrylate) (PMMA) particles in a poly(isobutylene) (PIB) matrix. These samples were then annealed above the glass transition temperature to promote latex film formation. Transmitted photon intensities, Itr, were measured for each film. It is observed that Itr decrease as the latex content is increased, which was explained by the increase in scattered light intensity, Isc. The drastic increase in Isc above a certain latex content is attributed to the site percolation of latex particles in the PIB matrix. The percolation threshold and the critical exponent were measured and found to be 0.3 and 0.4, respectively. The increase in Itr by annealing of film samples above Tg was explained with the void closure process below 0.8 occupation probability. When the film is occupied completely with the latex particles, interdiffusion of polymer chains was observed. Viscous flow and chain diffusion activation energies were determined and found to be 8 and 51 kcal/mol, respectively.

Journal Article↗