Synthesis of biodegradable polyhydroxyalcanoate copolymer from a renewable source by alternate feeding

Polyhydroxyalcanoates copolymers with 3-hydroxybutirate (3HB) and 3-hydroxyvalerate (3HV) co-monomers, P3(HB-co-x%HV), were produced in fed-batch culture by Ralstonia eutropha DSM428 using fructose as a single carbon source in the first step and adding propionic acid in the second step by alternating feeding. Polymer yield was 0.18 g/L with a content of 24 mol% of the 3HV fraction determined by H-1 NMR. NMR measurements indicated that the polymer obtained is isotactic. The copolymer attained 35% of crystallinity according to X-ray diffraction measurements, and two (020) planes were observed. Thermal behavior presented melting temperature at 154 degrees C and the crystallization temperature was 65 degrees C. A glass transition temperature was observed at -10 degrees C. Average molecular weight measured by GPC was 4.9 x 10(5) Dalton. Isothermal radial growth rates of spherulites of P3(HB-co-24%HV) were studied. All experimental facts and the analysis of the sequence distribution of diads and triads of 3HB and 3HV units led to the conclusion that it is not a completely statistical random copolymer once it contains different types of segments. POLYM.

Conformal deformation of equilibrium measures in normal random ensembles

We investigate the eigenvalue statistics of ensembles of normal random matrices when their order N tends to infinite. In the model, the eigenvalues have uniform density within a region determined by a simple analytic polynomial curve. We study the conformal deformations of equilibrium measures of normal random ensembles to the real line and give sufficient conditions for it to weakly converge to a Wigner measure.

Sparse block-Jacobi matrices with arbitrarily accurate Hausdorff dimension

We show that the Hausdorff dimension of the spectral measure of a class of deterministic, i.e. nonrandom, block-Jacobi matrices may be determined with any degree of precision, improving a result of Zlatos [Andrej Zlatos,. Sparse potentials with fractional Hausdorff dimension, J. Funct. Anal. 207 (2004) 216-252]. (C) 2010 Elsevier Inc. All rights reserved.

Nonlinear Schrodinger equation with chaotic, random, and nonperiodic nonlinearity

In this Letter we deal with a nonlinear Schrodinger equation with chaotic, random, and nonperiodic cubic nonlinearity. Our goal is to study the soliton evolution, with the strength of the nonlinearity perturbed in the space and time coordinates and to check its robustness under these conditions. Here we show that the chaotic perturbation is more effective in destroying the soliton behavior, when compared with random or nonperiodic perturbation. For a real system, the perturbation can be related to, e.g., impurities in crystalline structures, or coupling to a thermal reservoir which, on the average, enhances the nonlinearity. We also discuss the relevance of such random perturbations to the dynamics of Bose-Einstein condensates and their collective excitations and transport. (C) 2010 Elsevier B.V. All rights reserved.

Approach to Equilibrium for a Class of Random Quantum Models of Infinite Range

We consider random generalizations of a quantum model of infinite range introduced by Emch and Radin. The generalizations allow a neat extension from the class l (1) of absolutely summable lattice potentials to the optimal class l (2) of square summable potentials first considered by Khanin and Sinai and generalised by van Enter and van Hemmen. The approach to equilibrium in the case of a Gaussian distribution is proved to be faster than for a Bernoulli distribution for both short-range and long-range lattice potentials. While exponential decay to equilibrium is excluded in the nonrandom l (1) case, it is proved to occur for both short and long range potentials for Gaussian distributions, and for potentials of class l (2) in the Bernoulli case. Open problems are discussed.

Perturbation treatment of symmetry breaking within random matrix theory

We discuss the applicability, within the random matrix theory, of perturbative treatment of symmetry breaking to the experimental data on the flip symmetry breaking in quartz crystal. We found that the values of the parameter that measures this breaking are different for the spacing distribution as compared to those for the spectral rigidity. We consider both two-fold and three-fold symmetries. The latter was found to account better for the spectral rigidity than the former. Both cases, however, underestimate the experimental spectral rigidity at large L. This discrepancy can be resolved if an appropriate number of eigenfrequencies is considered to be missing in the sample. Our findings are relevant for symmetry violation studies in general. (C) 2008 Elsevier B.V. All rights reserved.

Theoretical Analysis of Aggregation in Block-Copolymer Films: The Optical Signature

We focus this work on the theoretical investigation of the block-copolymer poly [oxyoctyleneoxy-(2,6-dimethoxy-1,4phenylene-1,2-ethinylene-phenanthrene-2,4diyl) named as LaPPS19, recently proposed for optoelectronic applications. We used for that a variety of methods, from molecular mechanics to quantum semiempirical techniques (AMI, ZINDO/S-CIS). Our results show that as expected isolated LaPPS19 chains present relevant electron localization over the phenanthrene group. We found, however, that LaPPS19 could assemble in a pi-stacked form, leading to impressive interchain interaction; the stacking induces electronic delocalization between neighbor chains and introduces new states below the phenanthrene-related absorption; these results allowed us to associate the red-shift of the absorption edge, seen in the experimental results, to spontaneous pi-stack aggregation of the chains. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 885-892, 2010

Bose systems in spatially random or time-varying potentials

Bose systems, subject to the action of external random potentials, are considered. For describing the system properties, under the action of spatially random potentials of arbitrary strength, the stochastic mean-field approximation is employed. When the strength of disorder increases, the extended Bose-Einstein condensate fragments into spatially disconnected regions, forming a granular condensate. Increasing the strength of disorder even more transforms the granular condensate into the normal glass. The influence of time-dependent external potentials is also discussed. Fastly varying temporal potentials, to some extent, imitate the action of spatially random potentials. In particular, strong time-alternating potential can induce the appearance of a nonequilibrium granular condensate.

Synthesis of azopolymers with controlled structure and photoinduced birefringence in their LB films

The molecular architecture of azopolymers may be controlled via chemical synthesis and with selection of a suitable film-forming method, which is important for improving their properties for practical uses. Here we address the main challenge of combining the photoinduced birefringence features of azopolymers with the higher thermal and mechanical stabilities of poly(methyl methacrylate) (PMMA) using Atom Transfer Radical Polymerization (ATRP) to synthesize diblock- and triblock-copolymers of an azomonomer and the monomer methyl methacrylate. Langmuir-Blodgett (LB) films made with the copolymers mixed with cadmium stearate displayed essentially the same optically induced birefringence characteristics, in terms of maximum and residual birefringence and time for writing, as the mixed LB films with the homopolymer poly[4-(N-ethyl-N-(2-methacryloxyethyl))amino-2`-chloro-4`-nitroazobenzene] (HPDR13), also synthesized via ATRP. In fact, the controlled architecture of HPDR13 chains led to Langmuir films that could be more closely packed and reach higher collapse pressures than the corresponding films obtained with HPDR13-conv synthesized via conventional radicalar polymerization. This allowed LB films to be fabricated from neat HPDR13, which was not possible with HPDR13-conv. The enhanced organization in the LB films produced with controlled azopolymer chains, however, led to a smaller free volume available for isomerization of the azochromophores, thus yielding a lower photoinduced birefringence than in the HPDR13-conv films. The combination of ATRP synthesis and LB technology is then promising to obtain optical storage in films with improved thermal and mechanical processabilities, though a further degree of control must be sought to exploit film organization while maintaining the necessary free volume in the films. (C) 2008 Elsevier Ltd. All rights reserved.

Mixing alternating copolymers containing fluorenyl groups with phospholipids to obtain Langmuir and Langmuir-Blodgett films

The control of molecular architectures may be essential to optimize materials properties for producing luminescent devices from polymers, especially in the blue region of the spectrum. In this Article, we report on the fabrication of Langmuir-Blodgett (LB) films of polyfluorene copolymers mixed with the phospholipid dimyristoyl phosphatidic acid (DMPA). The copolymers poly(9.9-dioetylfluorene)-co-phenylene (copolymer I) and poly(9,9-dioctylfluorene)-co-quaterphenylene) (copolymer 2) were synthesized via Suzuki reaction. Copolymer I could not form a monolayer on its own, but it yielded stable films when mixed with DMPA. In contrast, Langmuir monolayers could be formed from either the neat copolymer 2 or when mixed with DMPA. The surface pressure and surface potential measurements, in addition to Brewster angle microscopy, indicated that DMPA provided a suitable matrix for copolymer I to form a stable Langmuir film, amenable to transfer as LB films, while enhancing the ability of copolymer 2 to form LB films with enhanced emission, as indicated by fluorescence spectroscopy. Because a high emission was obtained with the mixed LB films and since the molecular-level interactions between the film components can be tuned by changing the experimental conditions to allow For further optimization, one may envisage applications of these films in optical devices such as organic light-emitting diodes (OLEDs).

Solid-state NMR characterization of a series of copolymers containing fluorene, phenylene and thiophene units

Fluorene and thiophene units are commonly used in polymeric materials for electro-optical applications. Due to differences in reactivity, the final composition of polymers containing these components often differs from that used in their preparation. This contribution describes the synthesis of PPV type terpolymers built by fluorene, phenylene and thiophene units and their quantification by CPMAS NMR. The similarity of the three aromatic co-monomers makes it difficult to separate the analytical responses that would allow quantification of each copolymer unit in the chain. In this sense, we show that the combination of dipolar dephased CPMAS with radiofrequency ramp and proper spectral treatment allows a good estimation and quantification of the copolymer constitution. (C) 2011 Elsevier Ltd. All rights reserved.

Silsesquioxane as a New Building Block Material for Modified Electrodes Fabrication and Application as Neurotransmitters Sensors

Nanostructured films comprising a 3-n-propylpyridiniunn silsesquioxane polymer (designated as SiPy(+)Cl(-)) and copper (II) tetrasulfophthalocyanine (CuTsPc) were produced using the Layer-by-Layer technique (LbL). To our knowledge this is the first report on the use of silsesquioxane derivative polymers as building blocks for nanostructured thin films fabrication. Deposition of the multilayers were monitored by UV-Vis spectroscopy revealing the linear increment in the absorbance of the Q-band from CuTsPc at 617 nm with the number of SiPy(+)Cl(-)/CuTsPc or CuTsPc/SiPy(+)Cl(-) bilayers. FTIR analyses showed that specific interactions between SiPy+Cl- and CuTsPc occurred between SO(3)(-) groups of tetrasulfophthalocyanine and the pyridinium groups of the polycation. Morphological studies were carried out using the AFM technique, which showed that the roughness and thickness of the films increase with the number of bilayers. The films displayed electroactivity and were employed to detection of dopamine (DA) and ascorbic acid (AA) using cyclic voltammetry, at concentrations ranging from 1.96 x 10(-4) to 1.31 x 10(-3) molL(-1). The number and the sequence of bilayers deposition influenced the electrochemical response in presence of DA and AA. Using differential pulse technique, films comprising SiPy(+)/CuTsPc were able to distinguish between DA and ascorbic acid (AA), with a potential difference of approximately with 500 mV, in the concentration range of 9.0 x 10(-5) to 2.0 x 10(-4) molL(-1), in pH 3.0.

Paleomagnetic data and K-Ar ages from Mesozoic units of the Santa Marta massif: A preliminary interpretation for block rotation and translations

We report 6 K-Ar ages and paleomagnetic data from 28 sites collected in Jurassic, Lower Cretaceous and Paleocene rocks of the Santa Marta massif, to test previous hypothesis of rotations and translations of this massif, whose rock assemblage differs from other basement-cored ranges adjacent to the Guyana margin. Three magnetic components were identified in this study. A first component has a direction parallel to the present magnetic field and was uncovered in all units (D 352, I = 25.6, k = 57.35, a95 = 5.3, N = 12). A second component was isolated in Cretaceous limestone and Jurassic volcaniclastic rocks (D = 8.8, I = 8.3, k = 24.71, a95 = 13.7, N = 6), and it was interpreted as of Early Cretaceous age. In Jurassic sites with this component, Early Cretaceous K-Ar ages obtained from this and previous studies are interpreted as reset ages. The third component was uncovered in eight sites of Jurassic volcaniclastic rocks, and its direction indicates negative shallow to moderate inclinations and northeastward declinations. K-Ar ages in these sites are of Early (196.5 +/- 4.9 Ma) to early Late Jurassic age (156.6 +/- 8.9 Ma). Due to local structural complexity and too few Cretaceous outcrops to perform a reliable unconformity test, we only used two sites with (1) K-Ar ages, (2) less structural complexity, and (3) reliable structural data for Jurassic and Cretaceous rocks. The mean direction of the Jurassic component is (D = 20.4, I = -18.2, k = 46.9, a95 = 5.1, n = 18 specimens from two sites). These paleomagnetic data support previous models of northward along-margin translations of Grenvillian-cored massifs. Additionally, clockwise vertical-axis rotation of this massif, with respect to the stable craton, is also documented; the sense of rotation is similar to that proposed for the Perija Range and other ranges of the southern Caribbean margin. More data is needed to confirm the magnitudes of rotations and translations. (C) 2009 Elsevier Ltd. All rights reserved.

Random sums of exchangeable variables and actuarial applications

In this paper we study the accumulated claim in some fixed time period, skipping the classical assumption of mutual independence between the variables involved. Two basic models are considered: Model I assumes that any pair of claims are equally correlated which means that the corresponding square-integrable sequence is exchangeable one. Model 2 states that the correlations between the adjacent claims are the same. Recurrence and explicit expressions for the joint probability generating function are derived and the impact of the dependence parameter (correlation coefficient) in both models is examined. The Markov binomial distribution is obtained as a particular case under assumptions of Model 2. (C) 2007 Elsevier B.V. All rights reserved.

Random walks systems with killing on Z

We study random walks systems on Z whose general description follows. At time zero, there is a number N >= 1 of particles at each vertex of N, all being inactive, except for those placed at the vertex one. Each active particle performs a simple random walk on Z and, up to the time it dies, it activates all inactive particles that it meets along its way. An active particle dies at the instant it reaches a certain fixed total of jumps (L >= 1) without activating any particle, so that its lifetime depends strongly on the past of the process. We investigate how the probability of survival of the process depends on L and on the jumping probabilities of the active particles.