The Role of Pyranine in Characterization of PAAm-κC Composites by Using Fluorescence Technique

Polyacrylamide (PAAm) doped by κ-carrageenan (κC) gels were prepared with various amounts of κC varying in the range between 0 wt.% and 3 wt.%. Steady-state fluorescence (SSF) technique was employed for studying sol-gel transition and swelling of PAAm-κC composite gels which were prepared by free-radical crosslinking copolymerization. Pyranine was introduced as a fluorescence probe. 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 allow one to monitor the sol-gel transition and to test the universality of the sol-gel transition as a function of some kinetic parameters like polymer concentration. Observations around the gel point, t _c for PAAm-κC composite gels showed that the gel fraction exponent β obeyed the percolation result for low κC (<2.0 wt. %) however classical results were produced at higher κC (>2.0 wt.%). On the other hand, fluorescence intensity of pyranine was measured during in situ swelling process at various amounts of κC and it was observed that fluorescence intensity values decreased as swelling is proceeded. Li-Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D.     

Swelling Kinetics of PAAm–κ-Carrageenan Composites: A Fluorescence Technique

The steady-state fluorescence (SSF) technique was introduced for studying swelling of disc-shaped polyacrylamide (PAAm) gels containing various amount of κ?carrageenan (κC). They were prepared by free-radical cross-linking copolymerization. N,N^′-methylenebisacrylamide (BIS) and ammonium persulfate (APS) were added as a cross-linker and an initiator, respectively. Composite gels were prepared at 80°C with pyranine as a fluorescence probe. After drying of these gels, swelling kinetics were performed in water at 60°C by real-time monitoring of the pyranine fluorescence intensity, I, which decreased as swelling proceeded. The Li–Tanaka equation was used to determine the swelling time constants, τ ₁, and cooperative diffusion coefficients, D ₀, from fluorescence intensity, weight, and volume variations of the gels during the swelling processes in all cases. It was observed that τ ₁ decreased and D ₀ increased as the κC concentrations in the composites were increased indicating that high κC gels swell faster than low κC gels.     

Fractal Dimensions of κ-Carrageenan Gels during Gelation and Swelling

A photon scattering technique for research on the sol-gel and gel-sol transitions in κ-carrageenan-water systems with various carrageenan contents (CC) was utilized for characterizing the fractal dimensions during gelation and swelling. It was observed that the scattered photon intensity, I_sc, increased at all temperatures with an increase in the CC when I_sc was monitored against temperature. Additionally, the sol-gel transition temperatures were found to be much lower than the gel-sol transition temperatures, causing hysteresis of the phase transition loops. I_sc increased with an increase in CC at all test temperatures, which is attributed to the formation of a fractal-like carrageenan gel. After drying, the gels were used in swelling experiments where the gels were immersed in water at room temperature, reswelling to the original structure. It was observed that I_sc from the carrageenan gels increased as the CC was increased. The fractal dimension, d, during gelation was found to increase as the gelation temperature was increased. On the other hand, the d values during swelling decreased as the swelling time was increased.     

Dissolution of Al2O3-polystyrene latex composites: a fluorescence study

This work reports the use of the steady state fluorescence (SSF) technique to study dissolution of a composite film formed from a mixture of Al₂O₃ and polystyrene (PS) latex particles. The composite films were cast from dispersion of pyrene (P)-labeled PS particles in Al₂O₃ solution at room temperature and annealed at 280°C temperature for 10 min. Eight different composite films were studied in various latex contents. Toluene was used as dissolution agent. Fluorescence intensities I _P from P were monitored during dissolution. Fickian diffusion was employed to model the dissolution processes. Dissolution coefficients, D _d, were measured and found to be increased at high PS content in the composite films.     

Electrical,optical and fluorescence percolations in P(VAc-co-BuA)/MWCNT composite films

Effects of multiwall carbon nanotube (MWCNT) addition on the electrical conductivities, optical transparencies and fluorescence emissions of poly(vinyl acetate-co-butyl acrylate) (P(VAc-co-BuA))/MWCNT composite films were studied. Optical transmission, fluorescence emission and two point probe resistivity techniques were used to determine the variations of the optical, fluorescence and electrical properties of the composites, respectively. Transmitted photon intensity (I _tr), fluorescence emission intensity (I _fl) and surface resistivity (ρ _s) of the composite films were monitored as a function of MWCNT mass fraction (M) at room temperature. All these measured quantities of the composites were decreased by increasing the content of MWCNT in the composite. The conductivity and the optical results were attributed to the classical and site percolation theories, respectively. The fluorescence results, however, possessed both the site and classical percolation theories at low and high MWCNT content regions, respectively.     

Influence of Thomson effect on the resultant local Seebeck coefficient in thermoelectric composite materials

The resultant local Seebeck coefficient α _R (=α _S−α _T) at the interface of a thermoelement has not yet been measured, although it is an important factor governing the thermoelectric efficiency, where α _S is the local Seebeck coefficient and α _T is the one caused by the Thomson effect. It is shown in this paper that α _S, α _T, and α _R of the p- and n-type Cu/Bi–Te/Cu composites are obtained analytically and experimentally on the assumption that the local temperature of the composite on which the temperature difference ΔT is imposed varies linearly with changes in position along the composite. They were indeed estimated as a function of position from the local experimental data of R,ΔI,ΔT, and V generated by applying an additional current of ±I to the composite, where R is the electrical resistance and ΔI is a current generated by the composite. As a result, it was found that the absolute values of α _S at the hot interface of the p- and n-type composites are approximately 1.5 and 1.4 times higher than their lowest values in the middle region of the composite, respectively, while those of α _T are less than 8% of α _S all over the composite and are so small that the relation α _R≈α _S can be held. We thus succeeded in measuring α _R at the interfaces of the composite.     

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.     

The Harmonic Oscillator on Three-Dimensional Spherical and Hyperbolic Spaces: Curvature Dependent Formalism and Quantization

A nonlinear model representing the quantum harmonic oscillator on the three-dimensional spherical and hyperbolic spaces, S_k³S_{\kappa }^{3} (κ>0) and H_k³H_{k}^{3} (κ<0), is studied using geodesic spherical coordinates (r,θ,φ). The curvature κ is considered as a parameter and the results are formulated in explicit dependence of κ. The first part of the paper is concerned with the existence of Killing vectors, the existence of Noether symmetries and the properties of the Noether momenta. The second part is devoted to the transition from classical to quantum mechanics. The classical system is quantized by obtaining a κ-dependent invariant measure dμ _κ and expressing the Hamiltonian as a function of the Noether momenta.     

Husimi Operator for Describing Probability Distribution of Electron States in Uniform Magnetic Field Studied by Virtue of Entangled State Representation

For the first time we introduce an operator Δ _h (γ,ε;κ) for studying Husimi distribution function in phase space (γ,ε) for electron’s states in uniform magnetic field, where κ is the Gaussian spatial width parameter. The marginal distributions of the Husimi function are Gaussian-broadened version of the Wigner marginal distributions. Using the Wigner operator in the entangled state 〈λ | representation we find that Δ _h (γ,ε;κ) is just a pure squeezed coherent state density operator | γ,ε〉 _{κ κ} 〈γ,ε |, which brings much convenience for studying Husimi distribution, so we name Δ _h (γ,ε;κ) the Husimi operator. We then derive Husimi operator’s normally ordered form that provides us with an operator version to examine various properties of the Husimi distribution. Work supported by the National Natural Science Foundation under the grant: 10775097.     

Universality of sol--gel phase transition of κ-carrageenan in various salts: a steady state fluorescence study

Thermal phase transitions of κ-carrageenan in NaCl, KCl and CaCl₂ solutions were studied using steady state fluorescence (SSF) technique. Pyranine was introduced as a fluorescence probe for studying sol--gel phase transitions. Scattered light, I _sc and fluorescence intensity, I was monitored against temperature to determine the sol--gel (T _sg) phase transition temperatures. It was observed that T _sg values are strongly correlated to NaCl, KCl and CaCl₂ contents. The weight average degree of polymerization, DP _w and gel fraction G, exponents (γ and β) were measured and found to be in accord with the classical Flory--Stockmayer model, i.e., γ and β were found to be close to 1.0, independent of salt content.     

Spectral index and non-Gaussianity in supersymmetric hybrid inflation

We consider a supersymmetric hybrid inflation model with two inflaton fields. The superpotential during inflation is dominated by W=(κS+κ′S′)M ², where S, S′ are inflatons carrying the same U(1) _R charge, κ, κ′ are dimensionless couplings, and M (∼10¹⁵⁻¹⁶ GeV) is a dimensionful parameter associated with a symmetry breaking scale. One light mass eigenstate drives inflation, while the other heavier mass eigenstate is stuck to the origin. The smallness of the lighter inflaton mass for the scalar spectral index n _s ≈0.96, which is the center value of WMAP7, can be controlled by the ratio κ′/κ through the supergravity corrections. We also discuss the possibility of the two field inflation and large non-Gaussianity in this setup.     

Gadolinium scandate as an alternative gate dielectric in field effect transistors on conventional and strained silicon

Long channel n-type metal oxide semiconductor field effect transistors on thin conventional and strained silicon on insulator substrates have been prepared by integrating gadolinium scandate as high-κ gate dielectric in a gate last process. The GdScO₃ films were deposited by electron beam evaporation and subsequently annealed in oxygen atmosphere. Electrical characterization of readily processed devices reveals well behaved output and transfer characteristics with high I _on/I _off ratios of 10⁶–10⁸, and steep inverse subthreshold slopes down to 66 mV/dec. Carrier mobilities of 155 cm²/Vs for the conventional and 366 cm²/Vs for the strained silicon substrates were determined.     

A fluorescence study for the critical behavior of polymethylmethacrylate doped by multiwalled carbon nanotube (PMMA–MWNT) composite bulk gel systems

Polymethylmethacrylate (PMMA) doped by multiwalled carbon nanotube (MWNT) bulk gels were prepared with different amounts of MWNTs varying in the range between 1 and 20 wt%. Free-radical cross-linking copolymerization of PMMA–MWNT composite bulk gels was characterized by the steady-state fluorescence technique. Ethylene glycol dimethacrylate (EGDM) and pyrene (P _y ) were introduced as cross linker and fluorescence probe, respectively. Changes in the viscosity of the pregel solutions due to glass formation dramatically increased the P _y fluorescent intensities, which were used to study the glass transition of PMMA–MWNT composite gels for various MWNT contents. The fluorescence intensity of P _y is proportional to the average size of the glassy regions below and to the strength of the infinite network above the glass transition point. Observations around the glass transition point show that there are three regimes for MWNT concentration in which the gel fraction exponent, β, and the weight average degree of polymerization exponent, γ, differ drastically from percolation results, given in three dimensions as β=0.41 and γ=1.80.     

Thermal Phase Transitions of Agarose in Various Compositions: A Fluorescence Study

The effect of agarose content on thermal phase transitions of the agarose gels was investigated by using Steady State Fluorescence (SSF) method. Scattered light, I _sc and fluorescence intensity, I _fl were monitored against temperature during heating and cooling processes to investigate phase transitions. Two regions were observed during the heating and cooling processes. At the high temperature region, double helix to coil (h-c) transition took place. However, during the cooling process coil to double helix (c-h) transitions occurred at low temperature region. Transition energies were determined using the Arrhenius treatment, and found to be strongly correlated with the agarose content in the gel system. Transition temperatures were determined from the derivative of the sigmoidal transition paths and found to be increased by increasing agarose content in both cases.     

Effect of κ-carrageenan on volume phase transition for polyacrylamide (PAAm) hydrogel using the fluorescence technique

Steady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) gels with various content of κ-carrageenan (κC). Disc shaped composite hydrogels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with various amounts κC. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as crosslinker and initiator, respectively. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was monitored during in situ swelling processes of composite gels. It was observed that fluorescence intensity values decreased as swelling is proceeded. Li–Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D from intensity variations during the swelling processes. It was shown that swelling time constants, τ decreased and diffusion coefficients, D increased as the κC content in the composites are increased.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Critical behaviour in solutions of branched polymers and swollen gels as studied by static and dynamic light scattering

Summary We present results of static and dynamic light scattering study of the critical phenomena in semi-dilute solutions and gels of poly(methyl methacrylate) (PMMA) prepared by radical copolymerization of methyl methacrylate and ethylene dimethacrylate in the θ-solvent (4-heptanone). The correlation length ξ and the extrapolated zero-angle scattering intensityI _c,0 of the solutions with degree of cross-linkingf _c≤1% diverge at the pseudospinodal temperature with exponents ofv=0.5 and γ=1, respectively, characteristic of mean-field behaviour. The values ofv and y for samples withf _c≥1.5% are about 0.6 and 1.2, respectively, indicating that the phase transition in solutions of branched PMMA molecules and PMMA gels can be classified to the 3D Ising model. The pseudospinodal temperaturesT _s, for semi-dilute solutions of branched molecules and gels were found as a function of the degree of cross-linking,f _c. The time autocorrelation functions consist of two contributions of which the faster one is attributed to the cooperative motions of the polymer matrix, while the broad slow mode is due to the dynamics of the partly penetrating polydisperse clusters and can be interpreted in terms of a simple cluster diffusion model. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Focal switch of cosine-Gaussian beams

The focal switch of cosine-Gaussian (CsG) beams passing through a system with the aperture and lens separated is studied analytically and numerically. It is shown that the focal switch of CsG beams can appear not only for the apertured case, but also for the unapertured case. The necessary condition for the focal switch is that truncation parameter α > α_c and the beam parameter β > β_c, α_c, β_c being the corresponding critical values. There exists a maximum of the relative transition height Δz _sw as α varies, and Δz _sw increases with increasing β and decreasing N _w. The normalized axial intensity minimum I _min / I _max decreases with an increase of α and β, and I _min / I _max remains unchanged as N _w varies.     

Weak chaos and metastability in a symplectic system of many long-range-coupled standard maps

We introduce, and numerically study, a system of N symplectically and globally coupled standard maps localized in a d=1 lattice array. The global coupling is modulated through a factor r^-α, being r the distance between maps. Thus, interactions are long-range (nonintegrable) when 0≤α≤1, and short-range (integrable) when α>1. We verify that the largest Lyapunov exponent λ_M scales as λ_M ∝ N^-κ(α), where κ(α) is positive when interactions are long-range, yielding weak chaos in the thermodynamic limit N↦∞ (hence λ_M→0). In the short-range case, κ(α) appears to vanish, and the behaviour corresponds to strong chaos. We show that, for certain values of the control parameters of the system, long-lasting metastable states can be present. Their duration t_c scales as t_c ∝N^β(α), where β(α) appears to be numerically in agreement with the following behavior: β>0 for 0 ≤α< 1, and zero for α≥1. These results are consistent with features typically found in nonextensive statistical mechanics. Moreover, they exhibit strong similarity between the present discrete-time system, and the α-XY Hamiltonian ferromagnetic model.     

Formation and quenching mechanisms of excited particles in an oxygen-iodine laser medium

New values of a number of kinetic constants of processes proceeding in oxygen-iodine laser media are presented. The total probabilities of formation of I₂(X, 15 ≤ v ≤ 24) and I₂(X, 25 ≤ v ≤ 47) molecules in the course of quenching of I* atoms by I₂(X) are found to be 0.9 and 0.1, respectively. The quantum yield of singlet oxygen in the reaction O(¹ D) + N₂O → N₂ + O₂(a ¹Δ) is close to 100%. The quenching rate constants of I₂(A’) by O₂, H₂O, CO₂, I₂, and Ar and of I(² P _1/2) by O(³ P), O₃, NO₂, N₂O₄, and N₂O are presented.