Structural electrochemical study of hemoglobin by in situ circular dichroism thin layer spectroelectrochemistry

Secondary and tertiary or quaternary structural changes in hemoglobin (HB) during an electroreduction process were studied by in situ circular dichroism (CD) spectroelectrochemistry with a long optical path thin-layer cell. By means of singular value decomposition least-squares analysis, CD spectra in the far-UV region give two similar a components with different CD intensity, indicating slight denaturation in the secondary structures due to the electric field effect. CD spectra in the Soret band show a R --> T transition of two quaternary structural components induced by electroreduction of the heme, which changes the redox states of the center ion from Fe3+ to Fe2+ and the coordination number from 6 to 5. The double logarithmic analysis shows that electroreduction of hemoglobin follows a chemical reaction with R --> T transition. Some parameters in the electrochemical process were obtained: formal potential, E-0t = -0.167 V; electrochemical kinetic overpotential, DeltaE(0) = -0.32 V; standard electrochemical reaction rate constant, k(0) = 1.79 x 10(-5) cm s(-1); product of electron transfer coefficient and electron number, alphan=0.14; and the equilibrium constant of R --> T transition, K-c = 9.0.

Corona poling of liquid crystalline polymers with nitroazobenzene side chains

The orientational behavior of liquid crystalline polymers with para-nitro azobenzene as side chains under electric field was studied by UV-visible spectroscopy. The results showed that lambda(max) of the poled polymer films was around 394nm, compared to that of the unpoled films, the absorption decreased due to poling. The orientational parameters increased linearly with the increase of the electric field. The temporal stability of the poled polymer film is good at room temperature. This kind of materials showed promise application as nonlinear optical component in photorefractive polymers.

A STUDY OF THE SPECTRUM PROPERTIES AND THE PHOTOVOLTAGE RESPONSE OF NANOCRYSTALLINE ND2O3

The diffuse reflectance spectra of nanocrystalline Nd2O3 were measured in the ultraviolet-visible region, It is found that the part of f-->f transition bands were widened and red-shift occurred. The absorption tail-band in the region from 300 to 550 nm was assigned to the O-2p-->Nd-4f transition. The behavior of light-induced charge transfer and photovoltaic properties of nanocrystalline Nd2O3 were studied by the surface photovoltage spectroscopy (SPS) and electric field modulating SPS techniques. The SPS response shows two peaks at 330 nm(P-1) and 380 nm(P-2) in the UV-Vis range, The spectral features observed can be explained in terms of charge transfer and interband transition.

SYNTHESIS AND CHARACTERIZATION OF CROSS-LINKED 2ND-ORDER NONLINEAR-OPTICAL POLYMER

The present paper reports the synthesis of glycidyl monoether of 4-[(p-nitrophenyl) azo] phenol (GMNA) and crosslinking reaction of GMNA with hexamethylene diisocyanate biuret (HDIB). The Tg of crosslinked polymer was investigated by DSC. The orientation and stability of the poled and crosslinked polymer film were studied by UV-Vis spectra and Maker fringe method.

MOSSBAUER-EFFECT STUDIES OF A NEW ORGANOEUROPIUM COMPLEX [EU(ETA-6-C6ME6)(ALCL4)2]4

The Mossbauer spectrum of a new organoeuropium complex with a neutral pi-ligand, Eu(eta6-C6Me6) (AlCl4)2, is measured at 88 K. The Mossbauer parameters derived from the spectrum show the divalent nature of the europium ion in this organoeuropium complex. The calculations of the electric field gradient at the Eu nucleus in the crystal indicate that the Eu-Cl bond in the compound may possess a certain covalent character. The low Debye temperature of this complex may be attributed to weak and delocalized pi-bonding between the Eu atom and the benzene ring of hexamethylbenzene, and a slow paramagnetic relaxation is suggested by the Mossbauer effect.

SIMULATION OF THE OXYGEN-ATOM VACANCY IN THE HIGH-TEMPERATURE SUPERCONDUCTOR TIBA2CAN-1CUNO2N+2.5(N = 1)

These simulation calculations for the oxygen-atom vacancy in the high temperature superconductor TlBa2Ca(n-1)Cu(n)O2n+2.5(n = 1) have been performed by means of the tight-binding approximation based on the EHMO method. The results indicate that the effect of the oxygen-atom vacancy on the charge distributions at the Tl-, Ba-, Cu- and O-atom sites is appreciably different and that there may exist two kinds of Cu cation with different net charges (approximately + 3.0 or approximately + 1.0) due to the oxygen-atom vacancy in the lattice. The electric field gradient at the site of the oxygen-atom vacancy has been calculated. The position of the oxygen-atom vacancy which favours the high temperature superconductivity of TlBa2Ca(n-1)Cu(n)O2n+2.5(n = 1) has been discussed.

CALCULATIONS OF THE EIGENVALUES OF PURE QUADRUPOLE INTERACTION IN MOSSBAUER-EFFECT STUDIES

Two approximate formulae to calculate the eigenvalues of pure quadrupole interaction in Mossbauer effect studies have been proposed and the eigenvalue coefficients in the formulae have been given for various excited states and ground states of the nucleus with different spin. All the eigenvalues of pure quadrupole interaction between both excited state and ground state of nucleus with spin I = 3/2 divided-by 9/2 and the electric-field gradient with different asymmetry parameter (eta = 0 divided-by 1.0) have been calculated by these formulae. The results show that the accuracies in all the calculations are more satisfactory or same in comparison with those obtained by the formula of Shenoy and Dunlap, especially when the asymmetry parameter of electric-field gradient is larger than 0.8 for the nucleus with spin I = 5/2.

Dielectric response of graded spherical composites

We investigate the effective dielectric responses of graded spherical composites under an external uniform electric field by taking the dielectric function of spherical inclusion, epsilon(i) = cr(k) e(beta r), where r is the inner distance of a point inside the particle from the centre of the spherical particle in the coordination. In the dilute limit, our exact result is used to test the validity of differential effective dipole approximation (DEDA) for estimating the effective response of graded spherical composites and it is shown that the DEDA is in excellent agreement with the exact result.

Dielectric response of graded composites having general power-law-graded cylindrical inclusions

The dielectric response of graded composites having general power-law-graded cylindrical inclusions under a uniform applied electric field is investigated. The dielectric profile of the cylindrical inclusions is modeled by the equation epsilon(i)(r)=c(b+r)(k) (where r is the radius of the cylindrical inclusions and c, b and k are parameters). Analytical solutions for the local electrical potentials are derived in terms of hypergeometric functions and the effective dielectric response of the graded composites is predicted in the dilute limit. Moreover, for a simple power-law dielectric profile epsilon(i)(r) = cr(k) and a linear dielectric profile epsilon(i)(r) = c(b + r), analytical expressions of the electrical potentials and the effective dielectric response are derived exactly from our results by taking the limits b -> 0 and k -> 1, respectively. For a higher concentration of inclusions, the effective dielectric response is estimated by an effective-medium approximation. In addition, we have discussed the effective response of graded cylindrical composites with a more complex dielectric profile of inclusion, epsilon(i)(r)=c(b+r)(k)e(beta r). (c) 2005 American Institute of Physics.

Effective dielectric responses of graded composites of the particles with a general power-law gradation profile

The effective dielectric response of graded spherical composites having general power-law gradient inclusions is investigated under a uniform applied electric field, where the dielectric gradation profile of the spherical inclusions is modeled by the equation epsilon(i) (r) = c(b+r)(k). Analytical solutions of the local electrical potentials are derived in terms of hyper-geometric function and the effective dielectric response of the graded composites is predicted in the dilute limit. From our result, the local potentials of graded spherical composites having both simple power-law dielectric profile epsilon(i)(r) = cr(k) and linear dielectric profile epsilon(i) (r) = c(b+r) are derived exactly by taking the limits b --> 0 and k --> 1, respectively. In the dilute limit, our exact result is used to test the validity of differential effective dipole approximation (DEDA) for estimating the effective response of graded spherical composites, and it is shown that the DEDA is in excellent agreement with exact result. (C) 2005 Elsevier B.V. All rights reserved.

Dielectric responses of graded cylindrical composites

The effective dielectric responses of linear composites with graded cylindrical particles are investigated under an external uniform electric field. As an example, with the Kummer function, we have obtained the analytical solutions of electric potentials of graded composites with a cylindrical inclusion particle of dielectric function profile epsilon(i) = cr(k)e(betar), where r is the inside distance of a point in cylindrical particle from the original point of cylindrical coordinates. In the dilute limit, the effective dielectric response is derived by means of the mean field method. For larger volume fraction, we have estimated the dielectric response of the graded composites with an effective medium approximation. Furthermore, from our results, we have discussed the effective responses of graded composites for power-law and exponential dielectric function profiles, respectively. (C) 2004 Elsevier B.V. All rights reserved.

Effective dielectric response of composites witli graded material

The effective dielectric response of linear composites containing graded material is investigated under an applied electric field Eo. For the cylindrical inclusion with gradient dielectric function, epsilon(i)(r) = b + cr, randomly embedded in a host with dielectric constant epsilon(m), we have obtained the exact solution of local electric potential of the composite media regions, which obeys a linear constitutive relation D = epsilonE, using hypergeometric function. In dilute limit, we have derived the effective dielectric response of the linear composite media. Furthermore, for larger volume fraction, the formulas of effective dielectric response of the graded composite media, are given.

Effective dielectric response of graded spherical composites

The effective dielectric response of composites containing graded material is investigated when an external uniform electric field E-0 is applied to it. For a spherical particle with gradient dielectric constant, epsilon(i) (r) = b + cr, randomly embedded in a host with dielectric constant epsilon(m), we have obtained the exact solution of local electric potential in the composite media regions, which obey a linear constitutive relation D = epsilonE, using hypergeometric function. In dilute limit, the effective dielectric response of the linear graded composite media is derived. Furthermore, for larger volume fraction, we have given an effective medium approximation to estimate the effective dielectric response of the graded composite media. (C) 2003 Elsevier B.V All rights reserved.

Effective properties of graded elliptical cylindrical composites

The effective property has been investigated theoretically in graded elliptical cylindrical composite's consisting of inhomogeneous graded elliptical cylinders and an isotropic matrix under external uniform electric field. As a theoretical model, the dielectric gradient profile in the elliptical cylinder is modeled by a power-law function of short semi-axis variable parameter (xi(2) - 1) in the elliptical cylindrical coordinates, namely epsilon(i)(xi) = c(k) (xi(2) - 1)(k), where c(k) and k are the parameters, and xi is the long semi-axis space variable in an elliptical cylindrical inclusion region. In the dilute limit, the local analytical potentials in inclusion and matrix regions are derived exactly by means of the hyper-geometric function, and the formulas are given for estimating the effective dielectric responses under the external lfield along (x) over cap- and (y) over cap -directions, respectively. Furthermore, we have demonstrated that our effective response formulas can be reduced to the well-known results of homogeneous isotropic elliptical cylindrical composites if we take the limit k -> 0 in graded elliptical cylindrical composites. (c) 2006 Elsevier B.V. All rights reserved.

Effective properties of spherically anisotropic piezoelectric composites

Piezoelectric composites consisting of spherically anisotropic piezoelectric inclusions (i.e., piezoceramic material) in an infinite nonpiezoelectric matrix under a uniform electric field are theoretically investigated. Analytical solutions for the elastic displacements and the electric potentials are derived exactly. Taking account of the coupling effects of elasticity, permittivity, and piezoelectricity, formulas are derived for the effective dielectric and piezoelectric responses in the dilute limit. A piezoelectric response mechanism is revealed, in which the effective piezoelectric response vanishes irrespective of how much spherically anisotropic piezoelectric inclusions are inside. Moreover, the effective coupled responses of the piezoelectric composites show that the effective dielectric responses decrease (increase) as the inclusion elastic (piezoelectric) constants increase.