Synthesis and micellization of amphiphilic poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride) block copolymers

Amphiphilic biodegradable block copolymers [poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride)] were synthesized by the melt polycondensation of poly(ethylene glycol) and sebacic anhydride prepolymers. The chemical structure, crystalline nature, and phase behavior of the resulting copolymers were characterized with ¹H NMR, Fourier transform infrared, gel permeation chromatography, and differential scanning calorimetry. Microphase separation of the copolymers occurred, and the crystallinity of the poly(sebacic anhydride) (PSA) blocks diminished when the sebacic anhydride unit content in the copolymer was only 21.6%. ¹H NMR spectra carried out in CDCl₃ and D₂O were used to demonstrate the existence of hydrophobic PSA domains as the core of the micelle. In aqueous media, the copolymers formed micelles after precipitation from water‐miscible solvents. The effects on the micelle sizes due to the micelle preparation conditions, such as the organic phase, dropping rate of the polymer organic solution into the aqueous phase, and copolymer concentrations in the organic phase, were studied. There was an increase in the micelle size as the molecular weight of the PSA block was increased. The diameters of the copolymer micelles were also found to increase as the concentration of the copolymer dissolved in the organic phase was increased, and the dependence of the micelle diameters on the concentration of the copolymer varied with the copolymer composition. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1271–1278, 2006     

Synthesis and characterization of polyimides derived from (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides

A series of new polyimides were prepared via the polycondensation of (3‐amino‐2,4,6‐trimethylphenyl)‐(3′‐aminophenyl)methanone and aromatic dianhydrides, that is, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride. The structures of the polyimides were characterized by Fourier transform infrared and NMR measurements. The properties were evaluated by solubility tests, ultraviolet–visible analysis, differential scanning calorimetry, and thermogravimetric analysis. The two different meta‐position‐located amino groups with respect to the carbonyl bridge in the diamine monomer provided it with an unsymmetrical structure. This led to a restriction on the close packing of the resulting polymer chains and reduced interchain interactions, which contributed to the solubility increase. All the polyimides except that derived from BPDA had good solubility in strong aprotic solvents, such as N‐methyl‐2‐pyrrolidinone, N,N′‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfone, and in common organic solvents, such as cyclohexanone and chloroform. In addition, these polyimides exhibited high glass‐transition values and excellent thermal properties, with an initial thermal decomposition temperature above 470 °C and glass‐transition temperatures in the range of 280–320 °C. The polyimide films also exhibited good transparency in the visible‐light region, with transmittance higher than 80% at 450 nm and a cutoff wavelength lower than 370 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1291–1298, 2006     

Meshless simulation of equilibrium swelling/deswelling of pH‐sensitive hydrogels

Hydrogels have been widely used in microelectromechanical systems (MEMS) and Bio‐MEMS devices. In this article, the equilibrium swelling/deswelling of the pH‐stimulus cylindrical hydrogel in the microchannel is studied and simulated by the meshless method. The multi‐field coupling model, called multi‐effect‐coupling pH‐stimulus (MECpH) model, is presented and used to describe the chemical field, electric field, and the mechanical field involved in the problem. The partial differential equations (PDEs) describing these three fields are either nonlinear or coupled together. This multi‐field coupling and high nonlinear characteristics produce difficulties for the conventional numerical methods (e.g., the finite element method or the finite difference method), so an alternative—meshless method is developed to discretize the PDEs, and the efficient iteration technique is adopted to solve the nonlinear problem. The computational results for the swelling/deswelling diameter of the hydrogel under the different pH values are firstly compared with experimental results, and they have a good agreement. The influences of other parameters on the mechanical properties of the hydrogel are also investigated in detail. It is shown that the multi‐field coupling model and the developed meshless method are efficient, stable, and accurate for simulation of the properties of the stimuli‐sensitive hydrogel. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 326–337, 2006     

Electrochemical characteristics of gatifloxacin and its interaction with DNA.

The electrochemical behavior of gatifloxacin (GTFX) and its interaction with natural calf thymus DNA (ctDNA) is investigated by differential pulse voltammetry (DPV) on a carbon paraffined electrode. According to the suggested electrochemical equation, a binding constant of 1.7058 x 10(5) (mol L(-1))(-1) and binding sizes s = 3.09 (base pairs) of GTFX with ctDNA are obtained by nonlinear fit analysis of electrochemical data. The results demonstrate that GTFX has the properties of an intercalative binder.     

Effect of hydrogen loading on temperature/electric-field poling ofSiO2-based thin films on Si

Waveguide stacks of GeSiO₂-based glass deposited on Si exhibit a permanent second-order nonlinearity following temperature electric-field poling. High temperature hydrogen loading increases the second harmonic signal under certain conditions     

Invasiveness of LiTaO/sub 3/ and GaAs probes in external E-O sampling

Disturbances of signals on a coplanar waveguide (CPW) induced by the presence of LiTaO/sub 3/ and GaAs electrooptic probes in external electrooptic (EO) sampling have been simulated and compared quantitatively. The finite-difference-time-domain method is used to simulate the full wave field around a coplanar waveguide on a GaAs substrate in an external EO sampling configuration. The results indicate that the induced signal disturbance, or invasiveness, of a LiTaO/sub 3/ probe is almost ten times that of a GaAs probe in terms of the magnitude of S/sub 11/, but that LiTaO/sub 3/ yields about two times the EO response for a given S/sub 11/ and optical probing wavelength. The transparency of LiTaO/sub 3/ to shorter wavelengths, however, allows an even higher sensitivity for this material relative to GaAs. The results suggest that these probes do not exhibit significant invasiveness (magnitude of S/sub 11/ smaller than -40 dB), if they are removed from contact by the distance of CPWs center conductor width.<>     

Transversely polarized parton densities,their evolution and their measurement

The transverse spin asymmetry of a quark in a baryon and the linear polarization of a gluon in a vector meson are studied from thet-channel point of view. Using the Altarelli-Parisi approach, they are shown to obey independent evolution equations and to decrease with increasingQ ². We investigate the possibility to measure them at leading twist, to leading order in α and α_s and without analyzing the final polarizations. This requires simultaneous polarization of the beam and the target; the observable effect is in the azimuthal distribution of the highP _T particle or jet. Assuming a simple (quark+scalar diquark) model for the baryon, a large asymmetry is expected inp \(\bar p\) Drell-Yan collisions, a smaller one in highP _T pp collisions, from the interference term in the scattering of two identical quarks.     

Translational motion compensation for coronary angiogram sequences

A method of compensating for the lag of the video cameras typically used in angiographic systems is presented for use in sequences of digitized X-ray images. The lag effect is reduced by a straightforward weighted subtraction, which has the undesirable side effect of increasing noise. By superimposing several lag-corrected and appropriately shifted images, however, the signal-to-noise ratio can be restored. The algorithm uses the phase-correlation method to measure the two-dimensional shift of a mobile coronary arterial structure. Processing is confined to a rectangular area of interest (AOI), which encloses a feature of clinical significance. The differences of the phases of the Fourier transforms of two frames is computed, combined with an appropriate filter, and inverse Fourier-transformed to produce a phase-correlation image. The vector separation from the origin of image space of the peak of the phase-correlation image is the estimate of the shift of the artery's position in the second frame as compared to the first. The isolation of the AOI from the surrounding image is achieved by the application of a window and correction for any linear trend in the background intensity.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.