New technique of processing highly oriented poly(vinylidene fluoride) films exclusively in the β phase

Oriented β‐phase films were obtained by utilizing two different techniques: conventional uniaxial drawing at 80 °C of predominantly α‐phase films, and by drawing almost exclusively β‐phase films obtained by crystallization at 60 °C from dimethylformamide (DMF) solution with subsequent pressing. Wide angle X‐ray diffraction (WAXD) and pole figure plots showed that with the conventional drawing technique films oriented at a ratio (R) of 5 still contained about 20% of phase α, a crystallinity degree of 40% and β‐phase crystallographic c ‐axis orientation factor of 0.655. Drawing at 90 °C and with R = 4 of originally β‐phase films results in exclusively β‐phase films with crystallinity degree of 45% and orientation factor of 0.885. Crystalline phase, crystallinity degree, and crystallographic c‐axis orientation factor of both phases were also determined for α‐phase oriented films obtained by drawing α‐phase films at 140 °C. For films drawn at 140 °C the α to β phase transition drops to about 22%. Reduction in crystallinity degree with increasing R is more pronounced at draw temperature of 140 °C compared with 80 °C. Moreover, for both phases the c ‐axis orientation parallel to the draw direction is higher at draw temperature of 140 °C than at 80 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2793–2801, 2007     

First order phase equilibrium for classical bodies

Summary In this note the Author gives a general and unified treatment of first order phase equilibria for classical bodies like those considered by Truesdell and Toupin in[3].The Author reaches a system of partial differential equations (generalized Clapeyron equations) the conditions of whose solution are shown always to be satisfied.In particular, the Author derives the equations governing the polarized phase equilibrium for a fluid.Besides the equations ruling the phase equilibrium for a two phase n-component fluid mixture are given and the equivalence with the statical Gibbs-Duhem relation is shown.

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Sommario In questa nota l'Autore presenta una trattazione generale ed unificata degli equilibri di fase del primo ordine per corpi classici come quelli definiti da Truesdell e Toupin in[3].L'Autore perviene ad un sistema di equazioni alle derivate parziali (equazioni di Clapeyron generalizzate) del quale si dimostra la integrabilità.In particolare, si deducono le equazioni che governano gli equilibri di fase polarizzati.Inoltre si ottengono le equazioni che regolano l'equilibrio di fase per una miscela fluida a n componenti; in questo caso si dimostra l'equivalenza delle equazioni con la relazione statica di Gibbs-Duhem.

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This work was supported by the Gruppo Nazionale per la Fisica Matematica of C.N.R.     

Structure-activity-based design of a synthetic malaria peptide eliciting sporozoite inhibitory antibodies in a virosomal formulation

The circumsporozoite protein (CSP) of Plasmodium falciparum is a leading candidate antigen for inclusion in a malaria subunit vaccine. We describe here the design of a conformationally constrained synthetic peptide, designated UK-39, which has structural and antigenic similarity to the NPNA-repeat region of native CSP. NMR studies on the antigen support the presence of helical turn-like structures within consecutive NPNA motifs in aqueous solution. Intramuscular delivery of UK-39 to mice and rabbits on the surface of reconstituted influenza virosomes elicited high titers of sporozoite crossreactive antibodies. Influenza virus proteins were crucially important for the immunostimulatory activity of the virosome-based antigen delivery system, as a liposomal formulation of UK-39 was not immunogenic. IgG antibodies elicited by UK-39 inhibited invasion of hepatocytes by P. falciparum sporozoites, but not by antigenically distinct P. yoelii sporozoites. Our approach to optimized virosome-formulated synthetic peptide vaccines should be generally applicable for other infectious and noninfectious diseases.     

A mixed algorithm for the calculation of rapidly varying fluid flows: The impulsively started circular cylinder

A mixed discrete Fourier transform-Finite difference algorithm is developed and used for the calculation of rapidly changing viscous fluid flows past a circular cylinder. The numerical approach has been designed to overcome certain difficulties arising for high Reynolds number simulations. The foremost advantage of the technique lies in its fast calculations of the convolution sums portraying the convective terms of the governing equations. Third-order spatial discretizations and fourth-order time marching are implemented. New schemes are proposed for the boundary conditions at the solid wall and at large distances. The techniques are tested on a case study with other schemes (summarized by Roache¹) in order to obtain an optimal choice. Definite indications on the stability and accuracy of boundary condition schemes are achieved. Support for the statement of dominant importance of boundary conditions is also given. A comparison of computational results with experimental data is presented for the case study of the flow past an impulsively started cylinder at Reynolds number 20. The time development of the symmetrical zone of recirculation, which is formed at an early stage of the flow, has been studied for 300 ≤ Re ≤ 9500 by means of the proposed algorithm. Computational results, comparisons with experimental data² and discussion of upper limits of validity of the procedure will be presented in a companion paper.     

Properties of the blue-shifted emission of hematoporphyrin and related derivatives in aqueous solution

A blue-shift of the emission spectrum of hematoporphyrin and of its derivatives used in tumor phototherapy is shown to occur in water solutions. After 48 h incubation at 37°C, this emission becomes predominant, particularly in derivatives with a high degree of aggregation, and is characterized by a decay time of ≈2.6 ns. The appearance of this band, which is peaked at 580 nm, can be interpreted on the basis of a binding mechanism of monomers to stable aggregates.     

Smooth and discontinuous junctions in the p-system

Consider the p-system describing the subsonic flow of a fluid in a pipe with section a=a(x). We prove that the resulting Cauchy problem generates a Lipschitz semigroup, provided the total variation of the initial datum and the oscillation of a are small. An explicit estimate on the bound of the total variation of a is provided, showing that at lower fluid speeds, higher total variations of a are acceptable. An example shows that the bound on TV(a) is mandatory, for otherwise the total variation of the solution may grow arbitrarily.     

Arithmetical Rank of Squarefree Monomial Ideals Generated by Five Elements or with Arithmetic Degree Four

Let I be a squarefree monomial ideal of a polynomial ring S. In this article, we prove that the arithmetical rank of I is equal to the projective dimension of S/I when one of the following conditions is satisfied: (1) μ(I) ≤5; (2) arithdeg I ≤ 4.     

Oxygen‐Triggered Switchable Polymerization for the One‐Pot Synthesis of CO2‐Based Block Copolymers from Monomer Mixtures

Switchable polymerization provides the opportunity to regulate polymer sequence and structure in a one‐pot process from mixtures of monomers. Herein we report the use of O₂ as an external stimulus to switch the polymerization mechanism from the radical polymerization of vinyl monomers mediated by (Salen)Co^III?R [Salen=N,N′‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine; R=alkyl] to the ring‐opening copolymerization (ROCOP) of CO₂/epoxides. Critical to this process is unprecedented monooxygen insertion into the Co?C bond, as rationalized by DFT calculations, leading to the formation of (Salen)Co^III?O?R as an active species to initiate ROCOP. Diblock poly(vinyl acetate)‐b‐polycarbonate could be obtained by ROCOP of CO₂/epoxides with preactivation of (Salen)Co end‐capped poly(vinyl acetate). Furthermore, a poly(vinyl acetate)‐b‐poly(methyl acrylate)‐b‐polycarbonate triblock copolymer was successfully synthesized by a (Salen)cobalt‐mediated sequential polymerization with an O₂‐triggered switch in a one‐pot process.     

Effect of the nature of the metal atom on hydrogen bonding and proton transfer to [Cp*MH3(dppe)]: tungsten versus molybdenum

The hydrogen-bonding and proton-transfer pathway to complex [Cp*W(dppe)H(3)] (Cp*=eta(5)-C(5)Me(5); dppe=Ph(2)PCH(2)CH(2)PPh(2)) was investigated experimentally by IR, NMR, UV/Vis spectroscopy in the presence of fluorinated alcohols, p-nitrophenol, and HBF(4), and by using DFT calculations for the [CpW(dhpe)H(3)] model (Cp=eta(5)-C(5)H(5); dhpe=H(2)PCH(2)CH(2)PH(2)) and for the real system. A study of the interaction with weak acids (CH(2)FCH(2)OH, CF(3)CH(2)OH, (CF(3))(2)CHOH) allowed the determination of the basicity factor, E(j)=1.73+/-0.01, making this compound the most basic hydride complex reported to date. A computational investigation revealed several minima for the [CpW(dhpe)H(3)] adducts with CF(3)CH(2)OH, (CF(3))(2)CHOH, and 2(CF(3))(2)CHOH and confirms that these interactions are stronger than those established by the Mo analogue. Their geometries and relative energies are closely related to those of the homologous Mo systems, with the most stable adducts corresponding to H bonding with M-H sites, however, the geometric and electronic parameters reveal that the metal center plays a greater role in the tungsten systems. Proton-transfer equilibria are observed with the weaker proton donors, the proton-transfer step for the system [Cp*W(dppe)H(3)]/HOCH(CF(3))(2) in toluene having DeltaH=(-3.9+/-0.3) kcal mol(-1) and DeltaS=(-17+/-2) cal mol(-1) K(-1). The thermodynamic stability of the proton-transfer product is greater for W than for Mo. Contrary to the Mo system, the protonation of the [Cp*W(dppe)H(3)] appears to involve a direct proton transfer to the metal center without a nonclassical intermediate, although assistance is provided by a hydride ligand in the transition state.